CN101692503A - Battery pack and method for producing the same - Google Patents

Battery pack and method for producing the same Download PDF

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Publication number
CN101692503A
CN101692503A CN200910009842A CN200910009842A CN101692503A CN 101692503 A CN101692503 A CN 101692503A CN 200910009842 A CN200910009842 A CN 200910009842A CN 200910009842 A CN200910009842 A CN 200910009842A CN 101692503 A CN101692503 A CN 101692503A
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CN
China
Prior art keywords
battery
battery pack
polyalcohol
packaging material
polyisocyanates
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Granted
Application number
CN200910009842A
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Chinese (zh)
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CN101692503B (en
Inventor
山本鉴
瀬川健
斋藤俊介
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Murata Northeast China
Murata Manufacturing Co Ltd
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Sony Corp
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Publication of CN101692503A publication Critical patent/CN101692503A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/72—Encapsulating inserts having non-encapsulated projections, e.g. extremities or terminal portions of electrical components
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/134—Hardness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/136—Flexibility or foldability
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Battery Mounting, Suspending (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

A battery pack includes: a battery including a battery element covered with a packaging member, the battery element including a positive electrode and a negative electrode which are spirally wound together or stacked on one another through a separator; a protection circuit board for the battery; and a covering material collectively covering the battery and the protection circuit board. The covering material includes a shape-retaining polymer. The shape-retaining polymer contains an insulating curable polyurethane resin including polyol and polyisocyanate.

Description

Battery pack and preparation method thereof
The cross reference of related application
The application requires to submit on January 30th, 2008 benefit of priority of Japanese patent application 2008-19612 number of Japan Patent office, during whole disclosures of this application are incorporated herein as a reference.
Technical field
The present invention relates to comprise battery pack (battery pack) of rechargeable nonaqueous electrolytic battery and preparation method thereof.More specifically; the present invention relates to battery pack that comprises by battery and protectiveness circuit board and preparation method thereof; described battery and protectiveness circuit board and packaging material are integrated into parts; wherein said battery comprises the battery unit that is coated by package, and wherein this battery unit comprises that coiled coil is together or positive pole that piles up each other and negative pole each other via dividing plate.
Background technology
In recent years, various types of portable electric appts as camera integrated magnetic tape video tape recorder, portable phone and laptop computer, are put on market, and are developing the portable electric appts that those sizes are littler, weight is lighter.Because reducing of portable electric appts size and weight, the size and the weight that need have an energy that has increased and reduce as the battery pack of the compact power of electronic equipment.As the example of the battery that is used for this class battery pack, can mention lithium rechargeable battery with high power capacity.
Lithium rechargeable battery comprises battery unit, and this battery unit has the positive pole and the negative pole that can mix and go doped lithium ion, and wherein this cell seal is in metal can or metal level press mold, and by the control of the circuit board that is electrically connected with this battery unit.
Some known lithium rechargeable batteries constitute battery pack, this battery pack comprises battery unit and the circuit board that is sealed in metal can or the metal level press mold, and they all are contained in the shell with upper space separately and lower space (referring to for example patent document 1～3).
[patent document 1] JP 3556875
[patent document 2] JP 3614767
[patent document 3] JP 3643792
Summary of the invention
In above-mentioned known lithium rechargeable battery, the battery of cell seal in metal can realized easily high precision size degree, but this battery has the problem that cell thickness or weight may increase.
On the other hand, the thickness of the battery of cell seal in the metal level press mold and weight ratio adopt the battery of metal can little, but the problem of this battery is: the change in size of battery unit is big thereby be difficult to improve the precision size degree, and the mechanical strength of this battery is low.
In having the cells known group of lithium rechargeable battery, wherein said lithium rechargeable battery comprises battery unit that is sealed in metal can or the metal level press mold and the circuit board that is contained in the shell, in order to make battery and circuit board avoid external impact etc., require shell to have gratifying thickness.And, in the joint that utilizes two-sided tape or ultrasonic bonding that the upper and lower shell that separates is combined, each shell need have makes it the gratifying thickness being convenient to engage, and the thickness of whole battery group or weight increase inevitably, and the problem of this battery pack is that it is not suitable for compact power.
The invention solves the problems referred to above in the technology of developing.Such battery pack and preparation method thereof need be provided, and this battery pack is being favourable aspect high precision size degree and the high mechanical properties not only, and also is being favourable aspect reduction size and the weight.
At the problems referred to above, the inventor has carried out extensive research.Found that; the problems referred to above can so solve; the shape that promptly adopts special polyurethane resin to be integrated into as coating in the packaging material of the battery of single part and protectiveness circuit board keeps polymer (shape-retaining polymer), and finishes the present invention thus.
According to an aspect of the present invention; a kind of battery pack is provided; this battery pack comprises battery and packaging material, and described battery comprises by the battery unit of package coating and the protectiveness circuit board of battery, and described packaging material jointly coat battery and protectiveness circuit board.This battery unit comprises that coiled coil is together or positive pole that piles up each other and negative pole each other via dividing plate.These packaging material comprise that shape keeps polymer.This shape keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin comprises polyalcohol and polyisocyanates.
According to a further aspect in the invention, provide a kind of method for preparing battery pack, this method comprises the steps: the protectiveness circuit board of battery and battery is placed in the mold cavity; And will comprise resin and be expelled in the mold cavity that wherein comprises battery and battery protection circuit board and solidify this resin at interior sheathing material; form battery pack thus, make this battery pack be in the state that terminals reach this battery pack outside conductively with the packaging material that are used for jointly coating battery and protectiveness circuit board.Described battery comprises the battery unit that is coated by package, and wherein this battery unit comprises that coiled coil is together or positive pole that piles up each other and negative pole each other via dividing plate.Described resin is that shape keeps polymer, and this shape keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin comprises polyalcohol and polyisocyanates.
Foregoing of the present invention does not plan to describe each exemplary of the present invention or every kind of execution mode.Ensuing accompanying drawing more specifically illustrates these embodiments with specifying.
Description of drawings
Fig. 1 is the decomposition diagram of battery before coating with packaging material in battery pack according to embodiments of the present invention.
Fig. 2 is the perspective view that will coat and be contained in the structure of the battery unit among the package (laminated film) with package.
Fig. 3 A and 3B are the end-views of sidewall peripheral part of battery shown in Figure 1.
Fig. 4 A to 4C coats the exemplary top view of battery with the technology of formation battery pack with packaging material.
Fig. 5 A and 5B are the sectional views of battery pack.
Embodiment
Hereinafter in detail battery pack according to embodiments of the present invention will be described in detail.In this manual, with regard to concentration, content, quantity and other amount, " % " provides by quality, unless otherwise indicated.
Battery pack according to this embodiment comprises: battery, this battery comprise the battery unit that is coated by package, and wherein this battery unit comprises that coiled coil is together or positive pole that piles up each other and negative pole each other via dividing plate; The protectiveness circuit board of battery; And packaging material, these packaging material jointly coat battery and protectiveness circuit board.Described packaging material comprise that shape keeps polymer, and this shape keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin comprises polyalcohol and polyisocyanates.
In order to use the packaging material that comprise resin, general method is jointly to coat battery and protectiveness circuit board by molded hot melt method etc. with packaging material.In this case, select the thermoplastic resin of heating liquefaction and cooling curing for use, perhaps can wait the curable resin that solidifies by heating.
Yet thermoplastic resin has flowability when being heated to than high 50～150 ℃ temperature of its fusion temperature or glass transition temperature, therefore generally need be heated to up to 180～450 ℃.And thermoplastic resin places the time point of mould to begin to solidify at it, and therefore, if the moulded resin that preparation thickness reduces, the technology that near the resin that solidifies hand-hole in several seconds is poured in the large tracts of land by very narrow slit is disadvantageous.For this reason, for thermoplastic resin, than the battery pack that adopts metal can, even by being heated to high temperature when its viscosity is reduced, the injection pressure of resin also can increase, perhaps the number of hand-hole can increase in the mould, has large tracts of land and has the battery pack that is reduced to 250 μ m or littler thickness so be difficult to prepare, and can only prepare the battery pack of low volume energy density.
On the other hand, in order to adopt known thermosetting resin, curing temperature is up to about 150 ℃, and the cured thermoset resin is time-consuming, therefore adopts thermosetting resin to reduce productivity ratio.
The polyvinyl dividing plate that rechargeable nonaqueous electrolytic battery is used always is under 120～140 ℃ temperature closed (shut down) usually, and changes into the film of impermeable ion, thereby dividing plate may not have the effect of dividing plate.
The physical property that constitutes the electrolyte (as the polyvinylidene fluoride as nonaqueous electrolyte) of battery may change, and perhaps this variation may cause the battery distortion.
In addition,, also there is such possibility, promptly is added to the device such as the PCT (positive temperature coefficient of the conduct control assembly of work when current anomaly flows in the protective circuit about having the battery in the one of being molded in and the battery pack of protectiveness circuit board; Term " positive temperature coefficient " so mean makes cell resistance raise with temperature increases the characteristic that positive index variation occurs) device or temperature fuse damage, make the protectiveness circuit board can not play the effect of protectiveness circuit board.
According to embodiment of the present invention; the curable polyurethane resin that comprises the insulation of polyalcohol and polyisocyanates by utilization keeps polymer as the shape that constitutes packaging material; battery and protectiveness circuit board can coat with packaging material jointly at lower temperature (as 120 ℃ or lower); can not damage battery and protectiveness circuit board, so the battery pack that not only helps high precision size degree and high mechanical properties but also size that helps reducing and weight can be provided.
In addition, according to embodiment of the present invention, utilize the packaging material of the curable polyurethane resin that contains insulation, can improve the precision size degree, thereby make packaging material have less than the thickness of metallic plate and improve output, so can improve the energy density of gained battery pack.
And, according to embodiment of the present invention, utilize the packaging material of the curable polyurethane resin that comprises insulation, can boost productivity and provide excellent machinability, therefore can preparation size, shape, intensity etc. meet the battery pack of various application, and increase the degree of freedom of design.
Packaging material; Shape keeps polymer
The shape of the packaging material in the battery pack of formation the present embodiment keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin comprises polyalcohol and polyisocyanates.
Term used herein " the curable polyurethane resin of insulation " means such polyurethane resin, and it is formed on 25 ± 5 ℃ and the 65 ± 5%RH time specific insulations of measuring (Ω cm) is 10 10Ω cm or bigger cured product, it is 10 that the curable polyurethane resin of preferred this insulation forms specific insulation 11Ω cm or bigger cured product.And, more preferably the curable polyurethane resin of this insulation form dielectric constant be 6 or littler (1MHz) and dielectric breakdown voltage be 15kV/mm or bigger cured product.
Specific insulation is measured according to JIS C2105 method, wherein under 25 ± 5 ℃ and 65 ± 5%RH, the measuring voltage of 500V put on sample (thickness: 3mm), and in 60 seconds measurement volumes resistivity afterwards.
The polyalcohol that constitutes the curable polyurethane resin of insulation has preferred 30% or littler, and more preferably 20% or littler oxygen content.
When the oxygen content of polyalcohol is 30% or more hour, the physical property of gained cured product is not easy to change, have excellent humidity resistance and high-insulation, thereby the curable polyurethane resin that comprises the insulation of this polyalcohol can be advantageously used for the packaging material that constitute battery pack.
The oxygen content of polyalcohol (%) is determined by following formula:
The oxygen content of polyalcohol (%)=(be used for preparing the raw material oxygen of polyalcohol
Total weight)/(total weight of the raw material of polyalcohol) * (yield of polyalcohol)
The polyalcohol of the curable polyurethane resin of the insulation that constitutes has preferred 200 or littler, and more preferably 150 or littler iodine number.
When keeping the polyalcohol of polymer, the shape that is used to constitute packaging material has 200 or during littler iodine number; the gained cured product has the thermal endurance of excellence like this; even be placed in the hot environment; cured product is also non-sclerous or become fragile; thereby this curable polyurethane resin that comprises the insulation of polyalcohol can be advantageously used for packaging material, is used for jointly coating battery and protectiveness circuit board.
Iodine number is to measure according to the method described in the JIS K3331-1995.
About constituting the polyalcohol of the curable polyurethane resin that insulate, preferably use PEPA, PPG, the polyalcohol that main chain is made of carbon-carbon bond, perhaps their mixture.
PEPA is made of the product of aliphatic acid and polyalcohol, described aliphatic acid is preferably for example at least a following LCFA with hydroxyl that is selected from: ricinoleic acid, hydroxycaproic acid, hydroxydecanoic acid, the hydroxyl hendecanoic acid, hydroxylinolic acid, hydroxy stearic acid, and hydroxyl cetane acid (oxyhexanedecenoic acid).
Be preferably with the polyalcohol of fatty acid response and for example be selected from least a in following: glycol such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol or diethylene glycol (DEG), trifunctional polyalcohol such as glycerine, trimethylolpropane or triethanolamine, four sense polyalcohols are as two glycerine or pentaerythrite, six sense polyalcohol such as sorbierites, and eight sense polyalcohols such as maltose or sucrose.And example comprises the polyaddition products corresponding to the oxyalkylene of above-mentioned polyalcohol and aliphat, alicyclic or aromatic amine, and the polyaddition products of above-mentioned oxyalkylene and polyamide polyamines (polyamide polyamine).
In the middle of these, preferably use ricinoleic acid glyceride, ricinoleic acid and 1,1, the PEPA of 1-trimethylolpropane etc.
PPG is made of the alcohol and the polyaddition products of oxyalkylene, and described alcohol is preferably and for example is selected from least a in following: ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol, dihydroxylic alcohols is as 1,3-butanediol, 1,4-butanediol, 4,4 '-dihydroxyphenyl propane or 4,4 '-dihydroxyphenyl methane, and above alcohol such as the glycerine, 1,1 of ternary, 1-trimethylolpropane, 1,2,5-hexane triol or pentaerythrite.Described oxyalkylene is preferably and for example is selected from least a in following: ethylene oxide, propylene oxide, butylene oxide, and alpha-olefin oxide.
The polyalcohol that main chain is made of carbon-carbon bond is preferably and for example is selected from least a in following: the acrylic compounds polyalcohol, polybutadiene polyol, the polyisoprene polyalcohol, the hydrogenated butadiene polymer polyalcohol, polycarbonate polyol, by the polyalcohol that acrylonitrile (AN) or styrene monomer (SM) glycerol polymerization are obtained on the polyalcohol that is made of carbon-carbon bond, and polytetramethylene glycol (PTMG).
The preferred polyalcohol that constitutes the curable polyurethane resin of insulation comprises dusty material.
Because the dusty material that is comprised in the polyalcohol; so when coating battery and protectiveness circuit board jointly with packaging material; this comprises that the insulation curable polyurethane resin of the polyalcohol that contains dusty material and polyisocyanates has excellent thixotropy, and then has improved machinability.And, because the dusty material that comprised in the polyalcohol, utilize to comprise that the polyalcohol that contains dusty material and the formed packaging material of insulation curable polyurethane resin of polyisocyanates have the advantage that case hardness, thermal endurance and heat dissipation are improved.
The example of dusty material comprises the inorganic particle of calcium carbonate, aluminium hydroxide, aluminium oxide, silica, titanium oxide, carborundum, silicon nitride, calcium silicates, magnesium silicate or carbon, and such as the organic polymer particles of polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose, polyurethane or poly-phenol etc.These dusty materials can be used singly or in combination.The every kind of particle that constitutes dusty material can be through surface treatment, and can be the foaming powdery as the polyurethane or the poly-phenol of dusty material.In addition, dusty material comprises the dusty material of porous.
About constituting the polyisocyanates of the curable polyurethane resin that insulate, preferably use aromatic polyisocyanate, aliphatic polyisocyante, alicyclic polyisocyanates, perhaps their mixture.
The example of aromatic polyisocyanate comprises '-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene(poly)isocyanate (thick MDI), toluene di-isocyanate(TDI) (TDI), many methylenes benzene polyisocyanates (thick TDI), XDI (XDI), and naphthalene diisocyanate (NDI).
The example of aliphatic polyisocyante comprises hexamethylene diisocyanate (HDI).
The example of alicyclic polyisocyanates comprises isoflurane chalcone diisocyanate (IPDI).
More examples of polyisocyanates comprise the polyisocyanates by the carbodiimide modified that obtains with the above-mentioned polyisocyanates of carbodiimide modified, by the ester modified polyisocyanates of the isocyanuric acid that obtains with the chlorinated isocyanurates modified polyisocyanate, and molecular end has urethane (urethane) polymer of NCO, and it is the product of polyalcohol and excessive polyisocyanates.
These polyisocyanates may be used singly or in combin.
In the middle of these, preferably use '-diphenylmethane diisocyanate, polymethylene polyphenylene(poly)isocyanate, the perhaps polyisocyanates of carbodiimide modified.
The curable polyurethane resin of insulation can comprise catalyst to promote polyalcohol and the reaction of polyisocyanates or the dimerization or the trimerization of isocyanates.About described catalyst, can use to promote the known catalyst of above-mentioned reaction, the example comprises amine catalyst, forms the metallic catalyst of cyanurate, and organo-tin compound.
The example of amine catalyst comprises tertiary amine, as triethylenediamine, 2-methyl triethylenediamine, 4-methyl hexamethylene diamine, five methyl diethylentriamine, the pentamethyl dipropylenetriamine, the pentamethyl hexamethylene diamine, dimethylaminoethyl ether, trimethyl aminopropyl monoethanolamine, three-dimethylamino-propylhexahydrotriaz,ne, and tertiary amine salt.
The example that forms the metallic catalyst of cyanurate comprises the slaine of aliphatic acid, and its instantiation comprises dibutyl tin laurate, lead octoate, ricinoleic acid potassium, sodium ricinate, potassium stearate, odium stearate, potassium oleate, enuatrol, potassium acetate, sodium acetate, cyclic potassium naphthenate, sodium naphthenate, potassium octanoate, Sodium Caprylate, and their mixture.
When using the metallic catalyst that forms cyanurate, the chlorinated isocyanurates ring can be incorporated in the molecule of the curable polyurethane resin of insulation.Because have the chlorinated isocyanurates ring in the molecule, the gained cured product has advantageously improved anti-flammability and thermal endurance.
Preferably, the metallic catalyst that forms cyanurate is the amount use of 0.5～20 weight portion with scope, with respect to the polyalcohol of 100 weight portions.When the consumption of the metallic catalyst that forms chlorinated isocyanurates during, do not form gratifying chlorinated isocyanurates less than 0.5 weight portion.On the other hand, though when the consumption of the metallic catalyst that forms chlorinated isocyanurates with respect to the polyalcohol of 100 weight portions greater than 20 weight portions, can not obtain the effect that a large amount of catalyst like this is expected.
The example of organo-tin compound comprises the acetate tri-n-butyl tin, normal-butyl tin terchoride, stannous methide dichloride, dibutyl tin dichloride, and trimethyl tin hydroxide.
Catalyst can directly use, and also can use in the solution form in the solvent (as ethyl acetate), and described solution has 0.1～20% concentration, and adds with respect to the isocyanates of the 100 weight portions amount with 0.01～5 weight portion, by solid content.When catalyst directly used or uses with the solution form, catalyst was preferably 0.01～5 weight portion with respect to the addition of the isocyanates of 100 weight portions, is preferably 0.05～1 weight portion especially, by solid content.If catalyst consumption is too little as less than 0.01 weight portion, then the curing of polyurethane resin is too slow, is difficult to obtain resin state.On the other hand, if the addition of catalyst greater than 5 weight portions, then resin-shaped becomes extremely rapid, thereby is difficult to that resin mold is made the shape that constitutes the battery pack package material and keeps polymer.
Employed shape keeps polymer in the battery pack package material, except the curable polyurethane of insulation, the amount that can also not sacrifice curing performance comprises additive such as filler, fire retardant, defoamer, prevents microbial inoculum, stabilizer, plasticizer, thickener, mould inhibitor, perhaps other resin.
In additive, for example, with regard to fire retardant, can use triethyl phosphate, tricresyl phosphate (2,3-dibromo propyl ester) etc.
About other additive, can use filler such as antimony trioxide or zeolite, perhaps colouring agent such as pigment or dyestuff.
Packaging material; Packing material
Preferably, the packaging material that constitute battery pack can also comprise the packing material that comprises metal oxide, metal nitride etc. except that shape keeps polymer.Therefore, the shape that comprises the curable polyurethane resin of insulation keeps polymer preferably packing material to be had affinity, compatibility and reactivity.Also preferable shape maintenance polymer has excellent adhesion power and excellent size stability or the mouldability to the metal level press mold.
About packing material, can use ceramic packing, metal oxide filler, perhaps metal nitride filler.
The example of metal oxide filler or metal nitride filler comprises the oxide or the nitride of silicon (Si), aluminium (Al), titanium (Ti), zirconium (Zr), zinc (Zn) or magnesium (Mg), and any mixture of above-mentioned oxide or nitride.Metal oxide or metal nitride filler improve the hardness and the heat conduction of packaging material, the layer that comprises metal oxide filler or metal nitride filler can be arranged to contact with the layer that comprises shape maintenance polymer, also metal oxide filler or metal nitride filler can be mixed in the layer that comprises shape maintenance polymer.In this case, being dispersed in to preferable alloy oxide filler or metal nitride uniform filling shape keeps in the whole layer of polymer.
The amount of the packing material that is mixed can keep the type of polymer and suitably change according to shape, but preferred this amount is 3～60%, keeps the gross mass of polymer based on shape.When the amount of the packing material that is mixed less than 3% the time, the packaging material that may can not get having satisfactory hardness.On the other hand, when the amount of the packing material that is mixed greater than 60% the time, mouldability or brittleness of ceramics problem in then may occurring producing.
If the particle mean size of packing material is too little, then the hardness of packaging material increases, and the material filling of mould can be adversely affected when still molded, and this can cause the problem of productivity ratio aspect.On the other hand,, then be difficult to obtain needed intensity, so exist battery pack can not obtain the possibility of gratifying precision size degree if the particle mean size of packing material is too big.Therefore, packing material has preferred 0.5～40 μ m, the more preferably particle mean size of 2～20 μ m.
About the shape of packing material, can adopt different shape, as sphere, sheet, tabular and needle-like.Although have no particular limits, preferred spherical packing material is because its packing material for preparing easily and can low-cost obtain having even particle mean size; And preferably have the needle-like packing material of high aspect ratio, because this packing material improves intensity easily.The packing material of preferred sheet can improve filling capacity because work as when the amount of the packing material that is mixed increases.According to purposes or material, can mix and use packing material with different particle mean sizes or shape.
Packaging material can also comprise additive except shape keeps polymer and packing material.For example, can keep polymer to use curing agent, ultra-violet absorber, light stabilizer, perhaps their any mixture with shape.
The character of packaging material
Utilization contains the packaging material of the curable polyurethane resin of insulation as shape maintenance polymer, advantage according to the battery pack of this embodiment is that not only it has high precision size degree and high impact properties and high mechanical properties, and is that it can reduce size (thickness) and weight.
Preferred these packaging material have the physical property of numerical value as follows.
The packaging material that contain curable polyurethane resin (promptly the shape of insulation keeps polymer) have preferred 45～130 ℃, and more preferably 65～120 ℃, 75～110 ℃ glass transition temperature (Tg) most preferably, (DSC) measures by differential scanning calorimetry.
Preferably, packaging material have excellent impact resistance and excellent mechanical strength in routine operation, on the contrary, in abnormal operation, the easy perforate of packaging material, the gas that battery is produced is easy to leave battery pack.Keep polymer about the shape that constitutes above-mentioned packaging material, preferably use curable polyurethane resin.
In order to satisfy above-mentioned requirements, preferably, comprise shape and keep the packaging material of polymer to have such glass transition temperature, it equals or the temperature when being higher than the battery pack routine operation, and the temperature when being equal to or less than abnormal operation.
When glass transition temperature is lower than 45 ℃, comprise glass transition temperature that shape keeps the packaging material of polymer and may be lower than temperature in the routine operation, almost be unable to undergo to constitute in the routine operation warm-up movement that shape keeps the polymer of polymer, so be difficult to keep hardness, thereby disadvantageously be difficult to realize excellent mechanical strength.
On the other hand, if glass transition temperature is higher than 130 ℃, temperature when then comprising glass transition temperature that shape keeps the packaging material of polymer and may be higher than abnormal operation, stand and constitute the warm-up movement that shape keeps the polymer of polymer in the abnormal operation, so packaging material are perforate hardly, thereby disadvantageously be difficult to make the gas that produces in the abnormal operation battery pack that speeds away.
Comprise shape and keep the packaging material of polymer to have preferred 10～120MPa, more preferably 20～110MPa, most preferably the flexural strength of 70～100MPa is measured according to the plastics flexural property test method described in the JIS K7171.
Comprise shape and keep the packaging material of polymer to have preferred 30～3000MPa, more preferably 900～2550MPa, most preferably the flexural modulus of 1000～2500MPa is measured according to the plastics flexural property test method described in the JIS K7171.
Comprise shape and keep the packaging material of polymer to have preferred D30～D99, more preferably D60～D90, most preferably the case hardness of D60～D85 is measured according to the plastics scleroscope hardness test method described in the JIS K7215.
About Shore D, when packaging material have D30～D99, these packaging material advantageously have high impact properties and high mechanical properties.
Preferably, the Shore D of packaging material, the temperature when at abnormal operation be as when 60 ℃ or higher temperature are measured, and it is less than in (the Shore D of measurement in 23 ± 2 ℃ temperature and 50 ± 5%RH) of the reference environment described in the JIS K7215.If less than the hardness in normal running temperature, then packaging material are easily because the gas that produces in the abnormal operation and perforate, and when the packaging material perforate, can make this gas promptly leave battery pack in the hardness of abnormal operation temperature for packaging material.
Packaging material have the thickness of reduction, for example 1000 μ m or littler thickness at the packaged unit such as maximum one side of the employed rectangular cell of portable electric appts.
When the thickness of packaging material during, utilize the battery pack of this packaging material preparation to sacrifice the volume energy density index inevitably greater than 1000 μ m.
Packaging material further preferably have 300 μ m or littler thickness, and preferably have littler thickness, as long as can realize needed impact resistance of battery pack and mechanical strength.
When in packaging material, using shape to keep the combination of polymer and filler, intensity that intensity that is obtained in the time of can obtaining the combination than the use aluminum metal of routine or thermoplastic resin and metal and impact resistance are higher and more excellent impact resistance, therefore, when intensity that needs equate, can make the packaging material of thickness, and then improve volume energy density less than conventional packaging material.The packaging material that thickness increases are realized intensity and the reliability battery pack higher than conventional packaging material.In addition, the size and dimension of battery can at random be chosen, and this battery can be applicable to the battery of large-scale bicycle, automobile or back-up source, and has the freedom in the design, makes packaging material to be designed to the intensity that required part need have.
Referring now to accompanying drawing, describe and adopt the battery pack according to this embodiment of above-mentioned packaging material as follows.
Fig. 1 is the decomposition diagram before rechargeable nonaqueous electrolytic battery coats with packaging material in the battery pack according to embodiments of the present invention.
Among this figure, battery 20 comprises the battery unit 10 that is coated by the metal level press mold 17 as the package example, and this battery unit 10 is contained among the container part 17a (vacant part 17a) that is formed in the laminated film 17, and seals up the marginal portion of laminated film.In the present embodiment, vacant part 17a has the rectangular-plate-shaped space consistent with the battery unit 10 of rectangular plate shape.
About coating the package of battery unit 10, can use well-known metal level press mold, especially preferably use the aluminium lamination press mold.About the aluminium lamination press mold, the preferred film that is suitable for stretching and is suitable for forming the container part 17a that holds battery unit 10 that uses.
Preferably, the package that is used to coat battery unit 10 is by one deck, two-layer or more multi-layeredly constitute, and comprises polyolefin film.
For example, can use the aluminium lamination press mold with laminated construction, it comprises adhesive linkage and the sealer that is arranged in the aluminium lamination both sides.The preferred aluminium lamination press mold that uses makes, is a surperficial side from the inboard of battery unit 10, arranges the polypropylene layer (PP layer) as adhesive linkage, as the aluminium lamination of metal level, reaches nylon layer or PETG layer (pet layer) as sealer.
The structure of battery unit 10 is described below.
Fig. 2 is the perspective view that will coat and be contained in as the structure of the battery unit 10 in the laminated film 17 of package.In the figure, battery unit 10 comprises bar shaped positive pole 11, dividing plate 13a, with the anodal 11 bar shaped negative poles of arranging in opposite directions 12, and dividing plate 13b, they pile up each other and longitudinally coiled coil together, gel electrolyte 14 is applied to anodal 11 and negative pole 12 both sides separately.
Stretch out conductively and the anodal 11 positive terminal 15a that are connected and the negative terminals 15b that is connected with negative pole 12 (hereinafter being referred to as " electrode terminal 15 " unless otherwise indicated) from battery unit 10, and positive terminal 15a and negative terminals 15b are separately coated with sealant layer 16a and 16b (hereinafter generally being referred to as " sealant layer 16 " unless otherwise indicated), it is the resin sheet that maleic anhydride-modified polypropene (PPa) etc. constitutes, and is used to improve and the adhesion that coats the laminated film 17 of battery unit subsequently.
Each part of the above-mentioned battery of hereafter (before the packaging material coating).
Anodal
Positive pole comprises positive electrode active material layer, and this positive electrode active material layer contains positive active material and is formed at the both sides of positive electrode collector.Positive electrode collector is made of metal forming such as aluminium (Al) paper tinsel.On the other hand, positive electrode active material layer comprises, for example, and positive active material, conductive agent, and binding agent.Positive active material, conductive agent, binding agent, reaching solvent can any amount mix, as long as they disperse equably.
About positive active material, can use metal oxide, metal sulfide, perhaps specific polymer according to required cell types.For example, when forming lithium ion battery, can mainly use the composite oxides of lithium and transition metal, shown in following formula (1):
Li XMO 2 (1)
M represents at least a transition metal in the formula, and X is according to the charging of battery and discharge condition and change, and is generally 0.05～1.10.
About constituting the transition metal (M) of lithium composite xoide, can use cobalt (Co), nickel (Ni), manganese (Mn) etc.
The instantiation of lithium composite xoide comprises LiCoO 2, LiNiO 2, LiMn 2O 4, and LiNi yCo 1-yO 2(0＜y＜1).
Can use the solid solution that obtains with part transition metal in the another kind of element substitution lithium composite xoide, the example of this solid solution comprises LiNi 0.5Co 0.5O 2And LiNi 0.8Co 0.2O 2These lithium composite xoides can produce high voltage and have excellent energy density.As selection,, can use the metal sulfide or the oxide that do not contain lithium, as TiS about positive active material 2, MoS 2, NbSe 2Or V 2O 5These positive active materials can be used singly or in combination.
About conductive agent, can use material with carbon element, as carbon black or graphite.About binding agent, for example, can use polyvinylidene fluoride (PVDF) or polytetrafluoroethylene.About solvent, for example, can use the N-methyl pyrrolidone.
Positive active material, binding agent and conductive agent are mixed equably, make cathode mix, prepared cathode mix is dispersed in forms slurry in the solvent.Then, the gained slurry is coated on positive electrode collector equably by scraping the skill in using a kitchen knife in cookery etc., and desolvates to remove, then suppress, form positive electrode active material layer thus in high temperature is dry down.
Anodal 11 have the positive terminal 15a that links to each other with positive electrode collector one end by spot welding or ultrasonic bonding.Positive terminal 15a preferably is made of metal forming or net, but terminals can be made of any other material outside the metal, if this material be electrochemistry and chemically stable and can realize the conduction.The example that is used for the material of positive terminal 15a comprises aluminium.
Negative pole
Negative pole comprises negative electrode active material layer, and this negative electrode active material layer comprises negative electrode active material and is formed on the both sides of negative electrode collector.Negative electrode collector is made of metal forming such as copper (Cu) paper tinsel, nickel foil or stainless steel foil.
Negative electrode active material layer comprises, for example, and negative electrode active material, and optional conductive agent and binding agent.As positive active material, negative electrode active material, conductive agent, binding agent and solvent can any amount mix.
About negative electrode active material, can use the lithium metal, lithium alloy can mix or go the material with carbon element of elements doped lithium, perhaps the composite material of metal material and material with carbon element.
Can mix or go the instantiation of the material with carbon element of elements doped lithium to comprise graphite, be difficult to graphited carbon, and be easy to graphited carbon.More specifically, can use material with carbon element, as RESEARCH OF PYROCARBON, coke (pitch coke, needle coke or petroleum coke), graphite, vitreous carbon, the calcined product of organic high molecular compound (by obtaining) at proper temperature carbonized phenolic resin, furane resins etc., carbon fiber, perhaps active carbon.
And, about mixing or go the material of elements doped lithium, can use polymer such as polyacetylene or polypyrrole, perhaps oxide such as SnO 2
About can with the material of lithium alloyage, can use each metalloid, but often use tin (Sn), cobalt (Co), indium (In), aluminium, silicon (Si) or its alloy.When using the lithium metal, not necessarily need the lithium powder is mixed with binding agent with the formation coat film, and the method that can adopt wherein rolling lithium metal foil to combine by compacting and collector body.
About binding agent, for example, can use polyvinylidene fluoride or styrene butadiene rubbers.About solvent, for example, can be N-methyl pyrrolidone or methyl ethyl ketone.
Negative electrode active material, binding agent and conductive agent are mixed equably, make the negative pole mixture, prepared negative pole mixture is dispersed in forms slurry in the solvent.Then, the gained slurry is coated on negative electrode collector equably by the method identical with positive pole, and at high temperature drying is desolvated to remove, and then suppresses, and forms negative electrode active material layer thus.
Situation as anodal 11, negative pole 12 has the negative terminals 15b that is connected to collector body one end by spot welding or ultrasonic bonding, this negative terminals 15b can be made of any other material except that metal, as long as this material is in electrochemistry with chemically be stable and can realize conducting electricity.The example of the material of negative terminals 15b comprises copper and mickel.
Positive terminal 15a and negative terminals 15b stretch out from the same side conductively, and when battery unit 10 be that rectangular plate shape is for example as shown in Figure 2 the time, preferred positive terminal 15a and negative terminals 15b conductively from the same side (a normally Duan side) stretch out, but they can stretch out conductively from any side, only otherwise be short-circuited etc. and do not have adverse influence to get final product to battery performance.
About the joint of positive terminal 15a and negative terminals 15b, its bonding station and joint method are not limited to above-mentioned example, as long as can electrically contact.
Electrolyte solution
In electrolyte solution, can use electrolytic salt and nonaqueous solvents commonly used in the lithium ion battery.
The instantiation of nonaqueous solvents comprises the ethylene carbonate ester, propylene glycol carbonate, and gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, and by replace the solvent that the hydrogen in the above-mentioned carbonic ester obtains with halogen.These solvents can be used singly or in combination.
About lithium salts, can use the material that uses in the general cell electrolyte solution as the electrolytic salt example.Instantiation comprises LiCl, LiBr, LiI, LiClO 3, LiClO 4, LiBF 4, LiPF 6, LiNO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, LiAsF 6, LiCF 3SO 3, LiC (SO 2CF 3) 3, LiAlCl 4, and LiSiF 6From realizing the viewpoint of excellent oxidation stability, preferred LiPF 6Or LiBF 4These lithium salts can be used singly or in combination.
The concentration that is dissolved in the lithium salts in the nonaqueous solvents can be any concentration, as long as lithium salts can be dissolved in the above-mentioned nonaqueous solvents, but the concentration of lithium ion is 0.4～2.0mol/kg in the preferred nonaqueous solvents.
When adopting gel electrolyte, electrolyte solution matrix polymer gelling obtains gel electrolyte.
About matrix polymer, can use any polymer, this polymer is with to comprise the non-aqueous electrolytic solution that is dissolved in the electrolytic salt in the nonaqueous solvents compatible and can gelling.The example of matrix polymer comprises and comprises polyvinylidene fluoride in the repetitive, polyethylene glycol oxide, PPOX, polyacrylonitrile, the perhaps polymer of polymethacrylonitrile.These polymer can be used singly or in combination.
In the middle of these, preferred matrix polymer is that to introduce quantity in polyvinylidene fluoride or the polyvinylidene fluoride be 7.5% or the copolymer of littler hexafluoropropylene.This polymer has 5.0 * 10 usually 5～7.0 * 10 5The number-average molecular weight of (500000～700000) or 2.1 * 10 5～3.1 * 10 5The weight average molecular weight of (210000～310000) and the inherent viscosity of 1.7～2.1dl/g.
Dividing plate
Dividing plate is made of following material, for example, the perforated membrane that polyolefine material (as polypropylene (PP) or polyethylene (PE)) is made, the perhaps perforated membrane made of inorganic material (as ceramic fiber nonwoven fabric), and can constitute by the two-layer or more multi-layered perforated membrane that is stacked into layer structure.In the middle of these, may be more effective by the perforated membrane that polyethylene or polypropylene are made.
Usually, spendable dividing plate has preferred 5～50 μ m, the more preferably thickness of 7～30 μ m.When block board thickness was too big, the ratio of active material and dividing plate reduced, and reduce battery capacity, and the ionic conduction performance was poor, so current capability is bad.On the other hand, if block board thickness is too little, then the mechanical strength of separator membrane reduces.
The manufacturing of battery
The gel electrolyte solution of so preparation is coated on anodal 1l and the negative pole 12 equably, makes positive electrode active material layer and negative electrode active material layer all be impregnated with gel electrolyte solution, then it is stored at room temperature or drying, form gel electrolyte layer 14.
Then, utilize the positive pole 11 and the negative pole 12 that have gel electrolyte layer formed thereon 14 separately, positive pole 11, dividing plate 13a, negative pole 12 and dividing plate 13b are piled up mutually by this order, coiled coil forms battery unit 10 together then.
Subsequently, battery unit 10 is contained among container part (vacant part) 17a of laminated film 17, and coats, obtain the non-aqueous gel electrolyte secondary battery with this film.
In the present embodiment, as shown in figs. 1 and 2, battery unit 10 is by the top described laminated film 17 that is coated with, and with the heat-sealing of the film around the battery unit 10, forms battery 20.
With battery unit 10 usefulness aluminium lamination press molds, 17 coatings and with this film phonograph seal, press then shown in Fig. 3 A and the 3B, accommodate the part 17b (hereinafter often being referred to as " side seal part ") of the container part 17a both sides of battery unit 10 along the direction bending of container part 17a.
Preferably, angle of bend θ is 80～100 °.
When angle of bend during less than 80 °, the side seal part 17b of container part 17a both sides opens so wide, makes the width of battery 20 increase, thereby is difficult to reduce the size of battery 20 and improves battery capacity.100 ° of angle of bends as the upper limit are to determine according to the shape of container part 17a, and when accommodating platypelloid type battery unit 10 in the container part, are limited to about 100 ° on the angle of bend.The heat seal width of side seal part 17b is preferably 0.5～2.5mm, more preferably 1.5～2.5mm.
For the size and the raising battery capacity that reduce battery 20, the crooked width D of preferential side face seal part 17b is equal to or less than the height h of container part 17a or the thickness of battery unit 10.And for the size that reduces battery 20 and improve battery capacity, preferred crooked number is 1.
Next, description prepares the method for battery pack according to embodiments of the present invention.
In the method for preparation battery pack of the present invention; the rechargeable nonaqueous electrolytic battery of so preparation is placed mold cavity (die cavity) together with the protectiveness circuit board that can control cell voltage and electric current and pad; and utilize pad with battery and protectiveness circuit board layout the precalculated position in die cavity; then with comprising the sheathing material loading mould cavity that shape keeps polymer and packing material; and solidify this sheathing material, obtain being coated with the battery pack of packaging material thus.
The sheathing material that keeps polymer and packing material about the shape that comprises the curable polyurethane resin that contains insulation, in order to prevent that battery from suffering heat damage and enhance productivity, the temperature of sheathing material being injected die cavity is preferably room temperature to 120 ℃, more preferably room temperature to 90 ℃.
With sheathing material, particularly have in the process of full-bodied sheathing material loading mould cavity,, generally need use the sheathing material loading mould cavity when material imposes predetermined pressure in order to prevent to form the slit between this material and the chamber inner mold.
In this case, in order to prevent to be placed on battery in the die cavity and protectiveness circuit board, can adopt a lot of methods because of the sheathing material of filling of exerting pressure departs from preposition.Example as these methods; can mention the method that locator protrusions is provided in mould; and following method; wherein sheathing material divides two parts or more parts to add in the mold cavity; and battery and protectiveness circuit board can rest on the precalculated position of the part of not filling this material in the mold cavity, and then sheathing material is filled in the entire die chamber.
In addition, can also mention such method, wherein twine battery, and as positioning element, described adhesive tape, rubber strip or graticule mesh parts are covered with packaging material with battery and protectiveness circuit board with adhesive tape, rubber strip or graticule mesh parts.Also can mention following method, wherein sheet metal such as aluminium, iron or SUS plate are arranged in a side of battery, the other parts except that sheet metal are jointly with the sheathing material sealing, thus with battery and protectiveness circuit board location.
And; all right such method; battery and another member that constitutes battery pack comprising the battery unit that is covered with package; as the framework resin component or comprise the head components combination of bottom substrate; and the battery that will combine with this member and protectiveness circuit board be placed in the die cavity, makes them can remain on preposition in the mold cavity.
About the mould that uses in the above-mentioned embodiment, there is not concrete restriction, as long as can be arranged in the mold cavity coated with battery 20, protectiveness circuit board and the optional padded coaming (seeing below) that uses of aluminium lamination press mold 17.Mould generally has two or more casting nozzles, is used for the moulding material of after-hardening is incorporated into mold cavity.Therefore, in the gained battery pack, the excessive moulding material that solidifies according to casting nozzle remains in any part of packaging material.
In the present embodiment, excessive moulding material is trimmed, fill vestige and only stay slight resin.
Protective circuit generally is arranged in the top (referring to Fig. 1) of positive terminal 15a and negative terminals 15b.When battery 20 was rectangular plate shape (packaging material that will form are rectangle), padded coaming was arranged in a side or an opposite side or the both sides of stretching out terminals 15a and 15b conductively.
Particularly, in Fig. 1, padded coaming is arranged on the short side or two short sides of rectangular plate shape battery 20.
Protectiveness circuit board and padded coaming thus arranged are integrally molded by moulding material and battery 20.
Padded coaming is not only protected battery and protectiveness circuit board, and improves the impact resistance of gained battery pack.
Therefore, material as padded coaming, preferred resin such as Merlon, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, polypropylene or the polyethylene that use with impact resistance and excellent precision size degree, metal such as aluminium or stainless steel perhaps wherein have the resin material that embeds molded metal material such as aluminium.
Fig. 4 A～4C coats battery with the exemplary top view of formation according to the technology of the battery pack of the present embodiment with packaging material.
Battery 20 is arranged in protectiveness circuit board 32 and top side padded coaming 34 top side and bottom side padded coaming 33 is arranged in the bottom side, and place unshowned mould earlier along the dotted line bending shown in the figure (seeing Fig. 4 A and 4B).Then, in mould, inject the sheathing material that comprises shape maintenance polymer and filler, exert pressure and make it to this material simultaneously and solidify, obtain battery pack 30 (seeing Fig. 4 C) thus with the aluminium lamination press mold 17 that coats by packaging material 18 according to the present embodiment.
Sectional view along the gained battery pack 30 of the straight line intercepting that is parallel to the bottom is shown among Fig. 5 A, is shown among Fig. 5 B along the sectional view of the battery pack of electrode terminal intercepting.
In the above-described embodiment, the rechargeable nonaqueous electrolytic battery 20 that adopts gel electrolyte has been described, but the battery that embodiment of the present invention can be applicable to adopt the laminated film of electrolyte solution to coat.In this case, omit in the above-mentioned embodiment step that gel electrolyte is applied to anodal and negative terminal surface, and the step that will fill electrolyte solution is inserted in the heat seal step of laminated film.
More specifically,, inject electrolyte solution by remaining opening one side then, then seal this opening one side the three sides heat-sealing of the battery unit 10 of rectangular plate shape.Formed hermetic unit has rectangular frame shape generally.
According to embodiment of the present invention, can obtain such battery pack, the advantage of this battery pack is that not only it has high precision size degree and high mechanical properties, and is size and weight that it has reduction.This battery pack has the terminals that battery are connected to external electronic usually, but has omitted relevant explanation in the above-described embodiment.
According to embodiment of the present invention, employing comprises that the shape that contains insulation curable polyurethane resin keeps the packaging material of polymer, therefore the advantage of battery pack is that not only it has high precision size degree and high mechanical properties, and is size and weight that it has reduction.Therefore, this battery pack can be advantageously used for the battery of mobile electronic device such as portable phone, laptop computer, digital camera and hand-hold type video camera, the secondary cell of high-power applications such as electric automobile and hybrid vehicle, the perhaps battery of electric tool.
Embodiment
Hereinafter be described more specifically the present invention with reference to the following examples and Comparative Examples, it is restriction to scope of the present invention that these embodiment and Comparative Examples should not be construed as.
Embodiment 1～6
Adopt the curable polyurethane resin of insulation respectively, the polyalcohol and the polyisocyanates that constitute by carbon-carbon bond shown in each self-contained table 1 of this polyurethane resin.Polyalcohol and polyisocyanates are with 1: 2 ratio (polyalcohol: the polyisocyanates equivalent proportion) mix, and each other 90 ℃ of reactions 1 hour, the end that obtains insulating has the urethane prepolymer of NCO group.
When the polyisocyanates (polyisocyanates raw material 1 and polyisocyanates raw material 2) that uses two types, select the mixing ratio of polyisocyanates raw material 1 and polyisocyanates raw material 2, make that the number of OH group is identical with the number of NCO group in the polyisocyanates in the polyalcohol.
Next, preparation each film-covered battery shown in the table 1, and this battery is connected with the protectiveness circuit board that can control cell voltage and electric current with this state, embeds in mold cavity together with padded coaming and pad they and is fixed on the precalculated position.Then, be positioned at the resin hand-hole that aperture, mould top is 0.5mm from three, in die cavity, inject the sheathing material that contains the urethane prepolymer that insulate with temperature shown in the table 1, simultaneously to this material exert pressure (0.1MPa), and the time point of discharging from three resin taps that are positioned at the mould bottom at excess resin, solidify sheathing material in the die cavity forming packaging material, and will remain in the excess resin amputation in the tap, make the battery pack among each embodiment thus.
Embodiment 7～19
Obtain the urethane prepolymer that insulate respectively by the mode identical with embodiment 1～6, different is to adopt the curable polyurethane resin of the insulation of the pure and mild polyisocyanates of polyester polyols shown in each self-contained table 1 respectively.About PEPA, adopting the ratio of polyalcohol raw material 1 (aliphatic acid) and polyalcohol raw material 2 (polyalcohol) is the mixture of 80: 20 (weight ratio).
Obtain the battery pack of each embodiment respectively by the mode identical with embodiment 1～6, different is to adopt the urethane prepolymer of insulation respectively.
Embodiment 20～31
Obtain the urethane prepolymer that insulate respectively by the mode identical with embodiment 1～6, different is to adopt the curable polyurethane resin that comprises PPG shown in the table 2 and polyisocyanates insulation respectively.
About PPG, adopt polyalcohol raw material 1 (oxyalkylene) and polyalcohol raw material 2 (polyalcohol) with 80: 20 ratio (weight ratio) mixture.
In other words, about PPG, adopt the mixture of predetermined ratio, feasible (hydroxy number of each polyalcohol raw material 2 molecule)/(molecular weight of polyalcohol raw material 2)=(the oxyalkylene functional group number of each polyalcohol raw material 1 molecule)/(molecular weight of polyalcohol raw material 1), i.e. hydroxyl and oxyalkylene balance.
Obtain the battery pack of embodiment respectively by the mode identical with embodiment 1～6, different is to adopt the urethane prepolymer of insulation respectively.
Comparative Examples 1～4
Obtain the battery pack of Comparative Examples respectively by the mode identical with embodiment 1～6, different is to adopt the resin shown in the table 2 to keep polymer as shape respectively.In Comparative Examples 3, use the shape comprise thermoplastic acrylonitrile-butadiene-diene-styrene (ABS) resin to keep polymer, and will keep polymer-extruded with this polymer loading mould cavity in this shape of 120 ℃ of fusings.In Comparative Examples 4, use the shape comprise thermoplastic polyurethane to keep polymer, and will keep polymer-extruded with this polymer loading mould cavity in this shape of 110 ℃ of fusings.
About each battery pack in embodiment and the Comparative Examples, the sheathing material that constitutes packaging material has been shown in the table 1 and 2 has been injected into temperature in the die cavity, the curing time of sheathing material (being filled to the demoulding certainly), glass transition temperature (Tg) according to the differential scanning calorimetry measurement, Shore D according to the measurement of method described in the JIS K7215, according to flexural strength and the flexural modulus that method described in the JIS K7171 is measured, specific insulation, and the maximum ga(u)ge of packaging material one side.
The measurement of specific insulation (Ω cm)
Specific insulation is measured according to JIS C2105, in method of measurement under 25 ± 5 ℃ and 65 ± 5%RH to sample (area: 50mm * 50mm; Thickness: 3mm) apply the measuring voltage of 500V, after 60 seconds, with insulation resistance tester (SM-8220; HIOKI E.E.CORPORATION makes and sells) measurement volumes resistivity.
The measurement of thermoplastic resin hardness
About employed thermoplastic resin in the battery pack package material of Comparative Examples 3 and 4, hardness is measured according to JIS K6253, in method of measurement with two sample (areas: 50mm * 50mm; Thickness: 3mm) pile up (thickness: 6mm), and with hardometer (model: WR-105D; Nishi TokyoSeimitsu Co., Ltd. makes and sell) measure the hardness that this piles up sample.
And, about each battery pack in embodiment and the Comparative Examples, estimate battery performance by following method.The results are shown in table 1 and 2.
The evaluation of battery performance
(1) rated energy density (Wh/l)
At 23 ℃, carry out following circulation repeatedly: with the upper limit charging 15 hours of 4.2V and be discharged to the final voltage of 2.5V, and determine rated energy density by the discharge capacity of first circulation with the constant current of 1C and constant voltage.
Rated energy density (Wh/l)=(average discharge volt (V) * rated capacity (Ah))/battery volume
1C is meant the electric current that the theoretical capacity that makes battery in 1 hour is emitted.
(2) fall-down test (A)
In order to observe the variation of the mechanical strength of battery pack in embodiment and the Comparative Examples, ten battery pack of preparation in each example, and all ten battery pack are freely dropped on the concrete floor from 2 meters height.Each battery pack is carried out ten tests, makes six plane surfaces of battery pack clash into the floor respectively.To be designated as OK less than the battery pack number that damages, and battery pack number cracked or that moved by parts will be designated as NG.
(3) fall-down test (B)
About each embodiment and Comparative Examples, battery pack is freely fallen on the ground cement plate 50 times from 1.2 meters height, and measurement size changes (Δ t) then.
Figure G2009100098422D0000221
Figure G2009100098422D0000231
Figure G2009100098422D0000241
Figure G2009100098422D0000251
In the battery pack of the embodiment shown in table 1 and 2 1～31; the curable polyurethane resin that comprises the insulation of polyalcohol and polyisocyanates by employing keeps polymer as the shape that constitutes packaging material; battery and protectiveness circuit board can jointly coat with packaging material at lower temperature (as at 120 ℃ or lower); make battery and protectiveness circuit board not be subjected to brokenly ring; thereby can provide advantage not only to be to have high precision size degree and high mechanical properties, and be that size and weight with reduction make that thickness is 300 μ m or littler battery pack.In embodiment 1～31, the curing temperature of packaging material is 120 ℃ or lower, therefore, when avoiding the battery cause thermal damage, can also prepare the battery pack that production efficiency is improved, and for example can be short to 30 minutes or littler curing time.And each has the battery pack of embodiment 1～31 up to 500 (Wh/l) or bigger battery capacity.
On the contrary, by the results verification of fall-down test, Comparative Examples 1 and 2 battery pack all have long curing time and low mechanical strength.Comparative Examples 3 and 4 battery pack all do not have battery capacity.
Embodiment 32～44
Use the insulation curable polyurethane resin of polyalcohol shown in each self-contained table 3 and polyisocyanates respectively.Polyalcohol and polyisocyanates must arrive the urethane prepolymer that the end has the insulation of NCO group in the ratio reaction identical with embodiment 1～31.Prepare battery pack among these embodiment respectively by the mode identical with embodiment 1～31, different is to use the urethane prepolymer of described insulation respectively.
By the oxygen content and the iodine number of said method measurement polyalcohol, the results are shown in Table 3.About each battery pack among these embodiment, temperature when the sheathing material injection die cavity that constitutes packaging material has been shown in the table 3, the curing time of sheathing material (from being filled to the time of the demoulding), the maximum ga(u)ge of specific insulation and packaging material one side, and the evaluation of battery performance.
Figure G2009100098422D0000271
Figure G2009100098422D0000281
In the battery pack of the embodiment shown in the table 3 32～44, the polyalcohol that is comprised in the packaging material has oxygen content and the iodine number that is in preferable range respectively, thereby can prepare advantage and not only be to have high precision size degree and high mechanical properties, but also be that size and weight with reduction make that thickness is 300 μ m or littler battery pack.In embodiment 32～44, when avoiding the battery cause thermal damage, the battery pack that can provide production efficiency to be improved.And the battery pack of embodiment 32～44 has separately up to 500 (Wh/l) or bigger battery capacity.
According to embodiment of the present invention, owing to above-mentioned structure, can provide advantage not only to be to have high precision size degree and high mechanical properties, but also be to have the size of reduction and the battery pack of weight, and preparation method thereof.
It will be understood by those of skill in the art that in claim or the scope that is equal to it, can various modifications, combination, sub-combinations thereof and conversion occur according to designing requirement and other factors.

Claims (20)

1. battery pack comprises:
Battery, this battery comprise the battery unit that is coated by package, and this battery unit comprises that coiled coil is together or positive pole that piles up each other and negative pole each other via dividing plate;
The protectiveness circuit board of battery; And
Packaging material, these packaging material jointly coat described battery and protectiveness circuit board,
Wherein said packaging material comprise shape and keep polymer, and
Described shape keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin contains polyalcohol and polyisocyanates.
2. according to the battery pack of claim 1, the oxygen content of wherein said polyalcohol is 30% quality or littler.
3. according to the battery pack of claim 1, the iodine number of wherein said polyalcohol is 200 or littler.
4. according to the battery pack of claim 1, wherein said polyalcohol is to be selected from least a in following: PEPA, PPG, and the polyalcohol that is made of carbon-carbon bond of main chain.
5. according to the battery pack of claim 4, wherein said PEPA is made of the product of aliphatic acid and polyalcohol,
Wherein said aliphatic acid is at least a following LCFA with hydroxyl that is selected from: ricinoleic acid, and hydroxycaproic acid, hydroxydecanoic acid, the hydroxyl hendecanoic acid, hydroxylinolic acid, hydroxy stearic acid, and hydroxyl cetane acid, and
Wherein said polyalcohol is to be selected from least a in following: ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, diethylene glycol (DEG) comprises the trifunctional polyalcohol of glycerine, trimethylolpropane or triethanolamine, comprises four sense polyalcohols of two glycerine or pentaerythrite, comprise six sense polyalcohols of sorbierite, and comprise eight sense polyalcohols of maltose or sucrose.
6. according to the battery pack of claim 4, wherein said PPG is that the polyaddition products by pure and mild oxyalkylene constitutes,
Wherein said alcohol is to be selected from least a in following: ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol comprises 1,3-butanediol, 1,4-butanediol, 4,4 '-dihydroxyphenyl propane or 4,4 '-dihydroxyphenyl methane is at interior dihydroxylic alcohols, and comprise glycerine, 1,1,1-trimethylolpropane, 1,2,5-hexane triol or the pentaerythrite alcohol more than interior ternary, and
Wherein said oxyalkylene is to be selected from least a in following: ethylene oxide, propylene oxide, butylene oxide, and alpha-olefin oxide.
7. according to the battery pack of claim 4, the polyalcohol that wherein said main chain is made of carbon-carbon bond is to be selected from least a in following: the acrylic compounds polyalcohol, polybutadiene polyol, the polyisoprene polyalcohol, the hydrogenated butadiene polymer polyalcohol, polycarbonate polyol, and polytetramethylene glycol (PTMG).
8. according to the battery pack of claim 1, wherein said polyisocyanates is to be selected from least a in following: aromatic polyisocyanate, aliphatic polyisocyante, and alicyclic polyisocyanates.
9. battery pack according to Claim 8, wherein said aromatic polyisocyanate is to be selected from least a in following: '-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene(poly)isocyanate (thick MDI), toluene di-isocyanate(TDI) (TDI), many methylenes benzene polyisocyanates (thick TDI), XDI (XDI), and naphthalene diisocyanate (NDI).
10. battery pack according to Claim 8, wherein said aliphatic polyisocyante is hexamethylene diisocyanate (HDI).
11. battery pack according to Claim 8, wherein said alicyclic polyisocyanates are isoflurane chalcone diisocyanate (IPDI).
12. battery pack according to Claim 8, wherein said polyisocyanates is to be selected from least a in following: by the polyisocyanates of the carbodiimide modified that obtains with the carbodiimide modified polyisocyanates, by the ester modified polyisocyanates of the isocyanuric acid that obtains with the chlorinated isocyanurates modified polyisocyanate, and molecular end has the urethane polymer of NCO, and it is the product of polyalcohol and excessive polyisocyanates.
13. according to the battery pack of claim 1, wherein said packaging material are to comprise the composite material that shape keeps polymer and packing material.
14. according to the battery pack of claim 1, wherein said packaging material when measuring, have 45～130 ℃ glass transition temperature (Tg) according to differential scanning calorimetry (DSC).
15., when wherein said packaging material are measured according to the plastics flexural property test method described in the JIS K7171, have the flexural strength of 10～120MPa and the flexural modulus of 30～3000MPa according to the battery pack of claim 1.
16., when wherein said packaging material are measured according to the plastics scleroscope hardness test method described in the JIS K7215, have the case hardness of D30～D99 according to the battery pack of claim 1.
17. according to the battery pack of claim 1, the wherein said package that is used to coat battery unit is the aluminium lamination press mold.
18. according to the battery pack of claim 1, the wherein said package that is used to coat battery unit is by one deck, two-layer or film that multilayer is formed, and comprises polyolefin film.
19. a method for preparing battery pack, this method comprises the following steps:
The protectiveness circuit board of battery and battery is placed in the mold cavity, and described battery comprises the battery unit that package coats, and this battery unit comprises via the dividing plate coiled coil together or positive pole that piles up and negative pole; And
To comprise resin is expelled in the mold cavity that wherein comprises battery and battery protection circuit board and solidifies described resin at interior sheathing material; form battery pack thus with the packaging material that are used for jointly coating battery and protectiveness circuit board; make this battery pack be in the state that terminals reach this battery pack outside conductively
Wherein said resin is that shape keeps polymer,
Wherein this shape keeps polymer to comprise the curable polyurethane resin of insulation, and this polyurethane resin comprises polyalcohol and polyisocyanates.
20. according to the method for claim 19, the temperature that wherein said sheathing material is expelled in the mold cavity is 120 ℃ or lower.
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